Washing and cleansing agents with polyamides having improved dirtcarrying capacity

ABSTRACT

A WASHING AND CLEANSING COMPOSITION WITH IMPROVED DIRT-CARRYING CAPACITY CONSISTING ESSENTIALLY OF (1) A SURFACE-ACTIVE DETERGENT COMPOSITION, (2) FROM 0.1% TO 20% BY WEIGHT, BASED ON THE TOTAL SOLIDS, OR A WATER-SOLUBLE OR WATER-DISPERSIBLE POLYAMIDE REACTION PRODUCT OF (A) A POLYALKYLENEIMINE HAVING AN AVERAGE MOLECULAR WEIGHT OF FROM 300 TO 6000 SELECTED FROM THE GROUP CONSISTING OF POLYETHYLENEIMINES AND POLYPROPYLENEIMINES AND (B) AN ORGANIC POLYCARBOXYLIC ACID HAVING FROM 2 TO 10 CARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF OXALIC ACID, ALKANEDIOIC ACIDS, ALKANETRIOCI ACIDS, ALKENEDIOIC ACIDS, BENZENEDICARBOXYLIC ACIDS, BENZENETRICARBOXYL ACIDS, CYCLOHEXANEDICARBOXYLIC ACIDS, CYCLOHEXANETRICARBOXYLIC ACIDS, HYDROXYALKANEDIOIC ACIDS, HYDROXYALKANETRIOIC ACIDS, POLYOXYALKANEDIOIC ACIDS, POLYTHIOALKANEDIOIC ACIDS, POLYAMINOALKANEDIOIC ACIDS AND POLYAMINOALKANETRIOIC ACIDS, THE MOLAR RATIO OF ALKYLENEIMINE UNIT TO ORGANIC POLYCARBOXYLIC ACID BEING FROM 100:1 TO 5:1, AND (3) OPTIONALLY A NON-SURFACE-ACTIVE BUILDER SALT AND A COMPOUND WITH AN INTENSIFIED CLEANING ACTION.

3,663,444 WASHING AND CLEANSING AGENTS WITH POLYAMIDES HAVING IMPROVEDDIRT- CARRYING CAPACITY Edmund Schmadel, Mettmann, Germany, asslgnor toHenkel & Cie GmbH, Dusseldorf, Germany No Drawing. Filed Apr. 29, 1970,Ser. No. 33,09

Claims priority, application Germany, May 69,

P 19 22 450.1 Int. Cl. C11d 7/56 US. Cl. 252-99 6 Claims ABSTRACT OF THEDISCLOSURE A washing and cleansing composition with improveddirt-carrying capacity consisting essentially of (1) a surface-activedetergent composition,

(2) from 0.1% to 20% by weight, based on the total solids, of awater-soluble or water-dispersible polyamide reaction product of (a) apolyalkyleneimine having an average molecular weight of from 300 to 6000selected from the group consisting of polyethyleneimines andpolypropyleneimines and (b) an organic THE PRIOR ART It is known to addto washing and cleaning compositions which contain surface-activecompounds, substances which improve the dirt-carrying capacity of thewashing liquors. Such substances, subsequently called grayinginhibitors, prevent re-absorption of the detached dirt on the cleanedsurfaces. These substances are mostly polyanionic polymers, which areprepared either from natural substances such as cellulose, gelatine orglue or by polymerization of vinyl compounds such as acrylic acid,methacrylic acid, maelic acid and mixtures of these with copolymerizableolefins. The polysulfonates of vinyl polymers have also already beenrecommended as graying inhibiting additions to washing and cleaningcompositions. Of these compounds, however, only carboxymethylcellulosehas attained relatively great technical importance, chiefly since itsurpasses all known synthetic polymers in its graying-inhibiting action.Carboxymethylcellulose and the said synthetic polymers, however, havethe disadvantage that their graying-preventing action is restricted tocellulosic fibers. They are largely inactive in the washing of syntheticfibrous material, chemically altered cellulose or finished cottons. Thisdisadvantage becomes specially noticeable in the case of white textilesfrom polyester or polyolefin fibers, non-iron cottons and mixed fabricsfrom the said synthetic fibers and cellulose 3,663,444 Patented May 16,1972 fibers which, in spite of frequent washings, may become gray andconsequently of poor appearance.

OBJECTS OF THE INVENTION An object of the present invention is todevelop a composition which may not have the aforesaid disadvantages.

Another object of the invention is the development of a washing andcleansing composition with improved dirtcarrying capacity consisting ofessentially of (1) a surface-active detergent composition,

(2) from'-'0cl%-to..2.0%.-by weight, based on the total solids, of awater-soluble or water-dispersible polyamide reaction product of (a) apolyalkyleneimine having an average molecular weight of from 300 to 6000selected from the group consisting of polyethyleneimines andpolypropyleneimines and (b) an organic polycarboxylic acid having from 2to 10 carbon atoms selected from the group consisting of oxalic acid,alkanedioic acids, alkanetrioic acids, alkenedioic acids,benzenedicarboxylic acids, benzenetricarboxylic acids,cyclohexanedicarboxlic acids, cyclohexanetricarboxylic acids,hydroxyalkanedioic acids, hydroxyalkanetrioic acids, polyoxyalkanedioicacids, polythioalkanedioic acids, polyaminoalkanedioic acids, andpolyaminoalkanetrioic acids, the molar ratio of alkyleneimine unit toorganic polycarboxylic acid being from :1 to 5:1, and

( 3) optionally a non-surfaceacti-vebuilder saLt and aeorm pound with anintensified cleaning action.

These and other objects of the invention will become more apparent asthe description thereof proceeds.

DESCRIPTION OF THE INVENTION The invention provides a washing andcleansing composition with improved dirt-carrying capacity especiallyfor synthetic fibers comprising a surface-active detergent composition,froml0.1.%- to, 20%. by weight, based on the total solids, of awater-soluble or water-dispersible polyamide, which is obtained byreaction of a polyethyleneimine or 'polypropyleneimine of averagemolecular weight of from 300 to 6000 with a-di-, and/or tri-carboxylicacid containing 2 to 10 carbon atoms in the molecule and in which themolar ratio of alkyleneimine unit to polycarboxylic acid is from 100:1to 5:1, and 0ptionally a non-surface-active builder salt and a compoundwith an intensified cleaning action.

The polyamides contained in the new washing compositions are obtainableby known method. It is preferred to use polyethyleneimines as startingsubstances which have an average molecular weight from 300 to 6000,especially 500 to 3000. Suitable polycarboxylic acids having 2 to 10carbon atoms are aliphatic or cycloaliphatic, saturated or unsaturated,as well as aromatic, diand tricarhoxylie acids; such as alkanedioicacids carboxylic acids are polyoxyalkanedioic acids such as diglycolicacid; polythioalkanedioic acids such as thiodiglycolic acid;polyaminoalkanedioic acids such as iminodiacetic acid andpolyaminoalkanetrioic acids such as nitrilotriacetic acid. Mixtures ofthe above-mentioned carboxylic acids may also be used. The reactionproducts of polyethyleneimine with dicarboxylic acids are preferred.

The preparation of the polyamides is carried out in known way, forexample by heating the mixture of acid and polyalkyleneimine for severalhours in vacuo or in the presence of a solvent from which the waterformed in the reaction can be azeotropically distilled. Instead of thefree dior tri-carboxylic acids, their derivatives capable of reaction,for example the acid anhydrides, chlorides or bromides, may also be usedas starting substances. The amounts of dior tri-carboxylic acid used peralkyleneimine unit are preferably such that at least one mol of a diortri-carboxylic acid is associated with one macromolecule consisting ofpolyalkyleneimine. The molar ratio of alkyleneimine unit to polyvalentcarboxylic acid in the preferred range amounts to 50:1 to :1, dependingupon the average molecular weight of the polyalkyleneimine.

The polyamides prepared in the manner indicated have a resinousconsistency and are soluble or dispersible in water or in solutions ofwashing compositions. They may still contain minor amounts of unreactedstarting substances, which can be removed by extraction with organicsolvents and if desired again used in the reaction. Since thesecompounds do not affect the cleaning properties of the compositions,however, their separation is unnecessary. Owing to the insolubility ofthe high molecular weight compounds in organic solvents and on accountof their content of low-molecular weight fractions, the usual methods ofmolecular weight determination cannot be used. The degree ofpolymerization and molecular weight of the final polyamides thereforecannot be given with sufiicient accuracy.

In addition to the polyamides, the washing and cleaning compositionsaccording to the invention contain surface-active substances customaryin such compositions such as anionic, non-ionic or amphoteric detergentsubstances. Further, non-surface-active inorganic and/ or organicbuilder salts may be present, as well as compounds which increase thecleaning capacity of the compositions or the degree of whiteness of thetreated textiles.

Suitable detergent substances are anionic compounds of the sulfonate orsulfate type, for example alkylbenzene sulfonates; especiallyn-dodecylbenzenesulfonate, and also olefinsulfonates such as areobtained, for example, by sulfonation of primary or secondary aliphaticmonoolefins with gaseous sulfur trioxide and subsequent alkaline or acidhydrolysis. Alkylsulfonates, such as are obtainable from n-alkanes bysulfochlorination or sulfoxidation and subsequent hydrolysis orneutralization, or by addition of bisulfite to olefins, may also beused. In addition, a-sulfo-fatty acid esters, primary and secondaryalkyl sulfates and the sulfates of ethoxylated or propoxylated highermolecular weight alcohols are suitable.

Further compounds of this anionic class which, if desired, may bepresent in the washing compositions, are the higher molecular weightsulfated partial ethers and partial esters of polyhydric alcohols, suchas the alkali metal salts of the monoalkyl ethers or mono-fatty acidesters of glycerinemonosulfuric acid ester or1,2-dihydroxypropanesulfonic acid respectively. Sulfates of ethoxylatedor propoxylated fatty acid amides and alkylphenols and also fatty acidtaurides and fatty acid isothionates are also suitable.

Further suitable anionic detergent substances are alkali metal soaps ofhigher fatty acids of natural or synthetic origin, for example thesodium soaps of coconut, palm kernel or tallow fatty acids. Theamphoteric detergent substances may be alkylbetaines and especiallyalkylsulfobetaines, for example3-(N,N-dimethyl-N-alkylammonium)-propane-l-sulfonate and3-(N,N-dimethyl-N-alkylammonium) -2-hydroxypropanel-sulfonate.

The anionic detergent substances may be present as the sodium, potassiumand ammonium salts or as salts of organic bases, such as mono-, di ortri-ethanolamine. When the said anionic and amphoteric compounds containan aliphatic hydrocarbon residue, this should preferably be a straightchain and contain 8 to 22 carbon atoms. In compounds with an araliphatichydrocarbon residue the preferably unbranched alkyl chains contain anaverage of 6 to 16 carbon atoms.

The most suitable non-ionic surface-active detergent substances are 01glyegletherfierivatives of alcohols, fatty acids and a kylphenols whichcontain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in thehydrocarbon residue. Particularly suitable are polyglycol etherderivatives which contain from 5 to 15 ethylene glycol ether groups andof which the hydrocarbon residues are derived from straight chainprimary alcohols having 12 to 18 carbon atoms or from alkylphenols witha straight alkyl chain containing 6 to 14 carbon atoms. By addition of 3to 15 mols of propylene oxide to a last-named polyethylene glycol etheror by conversion into the acetals, washing substances are obtained whichare marked by a particularly low foaming power.

Further suitable non-ionic detergent substances are the water-solubleadducts, containing 20 to 250 ethylene glycol ether groups and 10 topropylene glycol ether groups of polyethylene oxide to polypropyleneglycol, ethylenediaminopolypropylene glycol and alkylpolypropyleneglycol with 1 to 10 carbon atoms in the alkyl chain. The said compoundsusually contain 1 to 5 ethylene glycol units per propylene glycol unit.Non-ionic compounds of the amineoxide and sulfoxide type which, ifdesired, may also be ethoxylated, are also utilizable.

Suitable mixing components are also inorganic cleaning salts orbuilders, especially condensed phosphates such as pyrophosphates,triphosphates, tetraphosphates, trimetaphosphates, tetrametaphosphatesand more highly condensed phosphates, in the form of the neutral or acidsodium, potassium or ammonium salts. Alkali metal triphosphates andtheir mixtures with pyrophosphate are preferably used. Further silicatesmay be used, especially sodium silicate, in which the ratio of Na OzsiOamounts to 1:3.5 to 1:1.

The condensed phosphates may also be wholly or partly replaced byorganic nitrogenor phosphorus-containing complex-forming substances witha cleaning action. These compounds include the alkali metal or ammoniumsalts of nitrilotriacetic acid, ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid and the higher homologues of the saidaminopolycarboxylic acids. Suitable homologues may be prepared, forexample, by polymerization of an ester, amide or nitrile of N-aceticacid aziridine and subsequent saponification to the carboxylic acidsalts, or by reaction of polyamines 'with a molecular weight of 500 to100,000 with salts of chloroacetic acid or bromoacetic acid in analkaline medium. Further suitable aminopolycarboxylic acids arepoly-(N-B-propionic acid)- ethyleneimines of average molecular weightfrom 500 to 200,000 which are obtainable analogously to the N-aceticacid derivatives. Phosphorus-containing complex-forming substances whichmay be used are the alkali metal and ammonium salts ofaminopolyphosphonic acids, especially aminotri-(methylenephosphonicacid), ethylenediaminetetra-( methylenephosphonic acid),1-hydroxyethane-1,ldiphosphonic acid, methylenediphosphonic acid,ethylenediphosphonic acid and the higher homologues of the saidpolyphosphonic acids. Mixtures of the aforesaid complexformingsubstances may also be used.

Further suitable mixing components are neutral salts such as sodiumsulfate and sodium chloride, and substances for regulating the pH suchas sodium or potassium bicarbonates, borates and hydroxides, and alsoacids such as lactic acid and citric acid. The quantity ofalkaline-reacting substances inclusive of the alkali metal silicates andphosphates should be such that the pH of a liquor suitable for coarsewashing amounts to 9 to 12 and for fine washing amounts to 6 to 9.

By suitable combination of different surface-active detergent substancesand builder salts, increased actions may be obtained in many cases, forexample, an improved washing power or a reduced foaming capacity. Suchimprovements are possible, for example, by combination of anionic withnon-ionic and/or amphoteric compounds, by combination of differentnon-ionic compounds or by mixtures of detergents of the same type whichdiffer in respect to the number of carbon atoms or the number andposition of the double bonds or branchings of the chains in thehydrocarbons. Likewise synergistically-acting mixtures of inorganic andorganic builder salts maye be used or combined with the aforesaidmixtures.

The compositions may contain oxygen-yielding bleaching agents, such ashydrogen peroxide, alkali metal perborates, alkali metal percarbonates,alkali metal perphosphates urea perhydrate and alkali metal pgrgulat oractive chlorine-containing compouns, I I rmtal hypochlorites,chlorinated trisodium phosph te and chlorinated cyanuric acid or itsalkali metal salts, according to the purpose of u Suitable opticalbrighteners are those of the bis(tri-"aiinyl)-4,4-diaminostilbenedisulfonic acid type of the formula precomppunds my be-presenw cially 2 to 4 carbon atoms, and in theheterocyclic ring Some of these brighteners are to be regarded astransitional types to the cotton brighteners as regards their afiinityfor the fiber, for example, the brightener in which R; equals NHC H Thecompound 4,4-bis-(4- phenyl-vicinal-triazolyl-Z-)-stilbenedisulfonicacid 2,2 also belongs to the cotton brighteners of thediaminostilbenesulfonic acid type.

In this formula Ar and Ar' signify aryl residues such as phenyl,diphenyl or naphthyl, which may be substituted by substituents such ashydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl,sulfonic acid and sulfonamide groups or halogen atoms. It is preferredto use a 1,3-diarylpyrazoline derivative in which the residue Arrepresents a p-sulfonamidophenyl group and the residue Ar represents ap'chlorophenyl group. Besides this, for brightening of other types offibers, suitable white toners may also be present, for example, those ofthe type of the naphthotriazolestilbenesulfonates, ethylenebisbenzimidazoles, ethylene bis benzoxazoles, thiophene bis benzoxazoles,dialkylaminocoumarins and cyanoanthracene. These brighteners or theirmixtures may be present in the compositions in amounts fromv 0.01 to1.5% by weight, preferably 0.1 to 1% by weight.

For the purpose of increasing the dirt carrying power, further knowngraying inhibitors may be added, such as sodium celluloseglycollate orthe water-soluble alkali metal salts of polyesters and polyamides orvinyl polymers containing free carboxyl groups. These include thepolyesters or polyamides from triand tetra-carboxylic acids and dihydricalcohols or diamines, and polymeric acrylic, methacrylic, maleic,fumaric, itaconic, citraconic and aconitic acids as well as the mixedpolymerizates of the said unsaturated carboxylic acids or theircopolymers with olefins.

Compositions which are intended for use in drum washing machinessuitably contain known foam-inhibiting agents, as, for example,saturated fatty acids with 20 to 24 carbon atoms, or their alkali metalsoaps, or triazine derivatives which are obtainable by the reaction of 1mol of cyanuric chloride with 2 to 3 mol of an aliphatic, straight,branched or cyclic chain, primary monoamine or by propoxylation orbutoxylation of melamine.

For further improvement of the dirt-loosening properties of thecompositions according to the invention, these may also contain Wheclass of proteases, lipases and amylases. The enzymes may be of animaland vegetable origin, for example may be obtained from digestiveferments or yeasts such as pepsin, pancreatin, trypsin, papain, catalaseand diastase. Enzymic active substances obtained from strains ofbacteria or fungi, such as Bacillus subtilis and Streptomyces griseus,are preferably used which are relatively stable towards alkali,per-compounds and anionic detergent substances and are not appreciablyinactivated even at temperatures between 45 and 70 C.

The washing and cleaning compositions may be present in liquid, pasty orsolid, for example pulverulent, granulated or lump form. Liquidpreparations may contain solvents miscible with water, especiallyethanol and isopropanol, and also solution aids such as the alkali metalsalts of benzene-, toluene-, xylene-, or ethylbenzenc-sulfonic acids. Toincrease the foaming capacity and to improve the compatibility with theskin, alkylolamides such as fatty acid monoand di-ethanolamides may beadded if desired. Moreover, the mixtures may contain dyestufis andperfumes, bactericides, substances with a freshening action, andfillers, for example urea.

The preparation of the compositions according to the invention may beeffected in the usual way by mixing, granulatmg or spray drying. Ifenzymes are used, it is advisable to mix these with non-ionic detergentsubstances and possibly perfumes or to disperse them in the melt of asalt containing water of crystallization, for example Glaubers salt, andthen to unite these prior mixtures with the remaining powder components.In this way the enzymes are cemented with the other particles of powderso that the mixtures do not tend to form dust or to separate into theircomponents.

The qualitative and quantitative composition of the preparationsaccording to the invention depend largely on their field of use. Thecontent of polyamide from polycarboxylic acid and polyalkyleneimineamounts to 0.1% to 20%, preferably 0.2% to 10% by weight based on totalsolids. The difference of 80% to 99.9%, preferably 90% to 99.8% byweight is composed of other washing agent components, the quantitativecomposition of which may correspond to the following scheme (data inpercent by weights):

1% to 40% of at least one compound from the class of the anionic,non-anionic and amphoteric surface-active compounds, preferably asutilizable in neutral to alkaline textile washing baths;

10% to 80% of at least one non-surface-active builder salt with acleaning intensifying action or a complexforming action;

10% to 50% of a pre-compound, especially sodium perborate, anhydrous orcontaining water of crystallization or its mixtures with stabilizers andactivators;

0.1% to 20% of other assistants and additives.

The surface-active compounds may consist of up to 100%, preferably 5% to70%, of anionic surface-active compounds of the sulfonate and/or sulfatetype; up to 100%, preferably 5% to 40%, of non-ionic surface-activecompounds of the polyglycol ether type; and up to 100%, preferably 10%to 50%, of soap.

The builder salts may be composed of up to 100%, preferably 25% to 95%,of alkali metal triphosphates and their mixtures with alkali metalpyrophosphates; up to 100%, preferably 5% to 50%, of an alkali metalsalt of a complex-forming substance from the class of polyphosphonicacids, nitrilotriacetic acid, ethylenediaminetetraacetic acid; and up to100%, preferably 5% to 75% of at least one compound from the class ofalkali metal silicates, alkali metal carbonates and alkali metalborates.

The other assistants and additives include, besides the opticalbrighteners, especially the foam inhibitors which may be present in thecompositions according to the invention in a quantity up to 5%,preferably in a quantity of from 0.2% to 3%, and also the enzymes whichmay be present in a quantity up to 5%, preferably 0.2% to 3%, and theadditional graying inhibitors, the amount of which may be up to 5%,preferably.0.2 t,o ,3%,

The present invention will be further described by way of reference tothe following specific examples which are not deemed limitative in anyrespect.

EXAMPLES ('1) A pulverulent, weakly foaming washing composition:

3% to 15% of a sulfonate detergent from the class ofalkylbenzenesulfonates, olefinsulfonates and n-alkanesulfonates,

0.5% to 5% of an alkylpolyglycol ether (C -C -alkyl) or an alkylphenolpolyglycol ether (C -C -alkyl) with 5 to 10 ethylene glycol ethergroups,

to of a C to C soap,

0.2% to 5% of a foam inhibitor from the class of trialkylmelamines andthe saturated fatty acids with 20 to 24 carbon atoms, or their alkalimetal soaps,

% to 50% of a condensed alkali metal phosphate from the class of pyroortri-polyphosphates,

0.1% to 5% of a polyamide reaction product of poly ethyleneimine anddior tri-carboxylic acids of the invention,

1% to 5% of sodium silicate 10% to 35% of sodium perborate tetrahydrate,

0 to 5% of enzymes,

0.05% to 1% of at least one optical brightener from the class ofdiaminostilbenedisulfonic acid and diarylpyrazoline derivatives.

0.1% to 30% of an inorganic salt from the class of thejlkalimetalwarbonates, bicarbonates, borates, sulfates 0 to 4% ofmagnesium silicate,

0.5 to 3% of sodium celluloseglycollate Examples 2-16 The grayinginhibiting action of the compounds described in the following exampleswas tested by the known soil redeposition method. In this method, 4small pieces from the fabric to be examined having a total weight of 8.3gm. together with 1.3 gm. of an artificially soiled cotton yarn arewashed three times for 30 minutes each time in a laboratory washingmachine. (Launder- Ometer," registered trademark.) The reflection valueis then found with a photometer (Elrepho, registered trademark) usingFilter N0. 6.

The combination of dust and skin fat similar to that found in practiceused for soiling the cotton yarn consisted of a mixture of kaolin, blackiron oxide, soot and synthetic skin fat (comprising /3 fatty acids, /3fat and V3 hydrocarbons). After soiling, the cotton yarn contained about1 1% of pigments and about 2% of skin fat.

A prior art washing preparation was used of the following composition(in percent by weight):

8% of n-dodecylbenzenesulfonate (Na salt) 3% of oleyl alcohol with 10ethylene glycol ether groups 3% of Na soap of saturated C to C fattyacids 40% of pentasodium tripolyphosphate 22% of sodium perborate 3.5%of sodium silicate (Na O:SiO =1:3.3)

2.5% of magnesium silicate 0.2% of Na nitrilotriacetate 0.3% of anoptical brightener 4% of graying inhibitors, as defined below, wereadded to this preparation and it was made up to 100% with sodiumsulfate.

The concentration of the washing composition used was 5 gm. per liter,and the hardness of the water was 10 German hardness. The textilesamples consisting of synthetic fabric (polyester fiber) and mixedfabric (polyester fiber with finished cotton and also polypropylenefiber with cotton) were washed at 60 C. and that of finished cotton waswashed at C. The proportion by weight of textile material to wash liquorwas 1:30. After a washing period of 30 minutes the samples were rinsedfour times with distilled water. After three washing treatments thedegree of whiteness of the samples was determined photometrically.

For the preparation of the graying inhibitors according to theinvention, a solution of the polyethyleneimine of the average molecularweight indicated and polycarboxylic acid, as indicated, in xylene washeated at the boil until 2 mols of water had been azetropicallydistilled per mol of polyvalent carboxylic acid. The resin remainingafter distilling the solvent was directly utilizable without furthertreatment.

The average molecular weight of the polyethyleneimine used, thepolycarboxylic used, and the molar ratio (mols of ethyleneimine unitsper mol of dior tri-carboxylic acid) are given in the following Table I,as well as the remission values of the washed textiles. For comparison,washing experiments were carried out without use of a graying inhibitorand with use of sodium celluloseglyeolrespectively, The results showafiisffifitfihperiority of the SltlOIlS according to the invention.

TABLE I Graying inhibitor Remission of values of the textile samplesAverage molecular Polyester Polyproweight of with pylene the polyethyl-Molar finished with Finished eneimlne Dlcarborylic acid ratio Polyestercotton cotton cotton 14:1 68. 9 66. 7 66.7 80. 1 1 28:1 ,60. 9 65.3 59.880. 6 1 42:1 58.? 60.6 641 81.7 14:1 58. 9 66.6 60.2 so. a 1 28:1 66.67. o 53. s 78.6 1 42: 1 6s. 6 61.4 58. a s2. 6 14: 1 58. 2 74. 7 69. 979. 4 1 28:1 69.3 76.3 63.0 76.2 1 42:1 60.3 63.9 62. 4 s2. 6 14:1 60.866. 4 59. 4 so. 6 1 28:1 67. 2 61.1 67. 6 77. 6 1 42:1 62. 1 63. 9 6s. 9s2. 6 14:1 67. 6 75. 3 48. 7 s1. 4 1 28:1 58.7 75.6 60.2 82.0 1 42: 1 6.97 74 a 60. 6 s1. 8

Without graying inhibitor 38.7 53. 1 35. 6 so. 7 Sodiumcelluloseglycollate 38. 9 53. 4 36. 0 60. 6

The preceding specific embodiments are illustrative of alkanedioicacids, polythioalkanedioic acids, polythe practice of the invention. Itis to be understood, howaminoalkanedioic acids and polyaminoalkanetrioicever, that other expedients known to those skilled in the acids, themolar ratio of alkyleneimine unit to orart, or described herein, may beemployed without deganic polycarboxylic acid being from 100:1 to 5:1.parting from the spirit of the invention or the scope of 2. The washingand cleansing composition of claim 1 the appended claims. wherein saidsurface-active compound of component (1) Iclaim: (a) is selected fromthe group consisting of sulfonates, 1. A washing and cleansingcomposition with improved sulfates, soap and polyglycol ethers.dirt-carrying capacity consisting essentially of 3. The washing andcleansing composition of claim 2 (1) from 80% to 99.9% by weight of adetergent comwherein said surface-active compound of component (1)position consisting essentially of (a) consists essentially of (i) from25% to 75% of said (a) from 1% to 40% of at least onesurface-acsulfonates and sulfates, (ii) from 5% to 40% of said tivecompound utilizable in neutral to alkaline polyglycol ethers, and (iii)from 10% to 50% of said textile washing baths selected from the groupsoaps. consisting of anionic surface-active compounds, 4. The washingand cleansing composition of claim 1 non-ionic surface-active compounds,amphoteric 40 wherein said non-surface-active builder salts ofcomposurface-active compounds, and mixtures thereof, nent (1) (b)consists essentially of (i) from 25% to 95% (b) from 10% to 80% of atleast one non-surof said alkali metal tripolyphosphates andpyrophosface-active builder salt which is an alkali metal phates, (ii)from 5% to 50% of said alkali metal salts salt of an acid selected fromthe group consistof said polyphosphonic acids, said nitrilotriaceticacid ing of tripolyphosphoric acid, pyropbosphoric and saidethylenediaminetetraacetic acid, and (iii) from acid, polyphosphonicacids, nitrilotriacetic acid, 5% to 75 of said alkali metal silicates,carbonates and ethylenediaminetetraacetic acid, silicic acid,carborates. bonic acid and boric acid, 5. The washing and cleansingcomposition of claim 1 (c) from 10% to of a bleaching compound whereinsaid bleaching compound of component (1) (c) selected from the groupconsisting of per-com- 50 is selected from the group consisting ofanhydrous sodipounds and mixtures of per-compounds with um pgrborgte andwater-of-crystallization-containing sostabilizers and activators, diumperborate.

(d) from 0.1% to 20% of other customary wash- 6. The washing andcleansing composition of claim 1 ing composition assistants andadditives includwherein said other customary washing composition asingat least one of from 0.2% to 5% enzymes, sistants and additives ofcomponent (1)(d) include from from 0.2% to 5% of customary grayinginhibi- 0.2% to 5% of at least one foam inhibitor selected from tors,and from 0.01% to 1.5% of optical the group consisting of saturatedfatty acids containing 20 brighteners and, to 22 carbon atoms and theiralkali metal soaps, substi- (2) from 0.1% to 20% by weight, based on thetotal tuted triazines obtained by reaction of 1 mol of cyanuric sol-ids,of a water-soluble or water-dispersible polychloride with 2 to 3 mols ofa primary monoamine and amide reaction product of (a) apolyalkyleneimine propoxylation and butoxylation products of melamine.having an average molecular weight of from 300 to 6000 selected from thegroup consisting of polyethyl- References Cited eneimines andpolypropyleneimines and (b) an or- UNITED STATES PATENTS ganicpolycarboxylic acid having from 2 to 10 carbon atoms selected from thegroup consisting of g fifigg f 3' 5 5; oxalic acid, alkanedioic acids,alkanetrioic acids, e alkenedioic acids, bengenedicarboxylic acids, ben-MAYER WEINBLATT, Primary Examiner zenetricarboxylic acids,cyelohexanedicarboxyhc US Cl R acids, cyclohexanetricarboxylic acids,hydroxyalkanedioic acids, hydroxyalkanetrioic acids, polyoxy- 252525,544, DIG 2, DIG 15; 260-78 TF, 78 A, EN

